EP1838772B1 - Method for transformation of conventional and commercially important polymers into durable and rechargeable antimicrobial polymeric materials - Google Patents

Method for transformation of conventional and commercially important polymers into durable and rechargeable antimicrobial polymeric materials Download PDF

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EP1838772B1
EP1838772B1 EP06717982.0A EP06717982A EP1838772B1 EP 1838772 B1 EP1838772 B1 EP 1838772B1 EP 06717982 A EP06717982 A EP 06717982A EP 1838772 B1 EP1838772 B1 EP 1838772B1
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tetramethyl
piperidyl
polymer
imino
poly
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EP1838772A2 (en
EP1838772A4 (en
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Yuyu Sun
Zhaobin Chen
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University of Texas System
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University of Texas System
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides

Definitions

  • the present invention relates in general to the field of antimicrobials, and more particularly, to compositions and methods to make and recharge antimicrobial additives for polymeric materials.
  • antimicrobial polymers polymers that can effectively inactivate microorganisms upon contact
  • the simplest and most cost-effective method in the preparation of antimicrobial polymeric materials is to directly add antimicrobial additives into polymer structures during processing and has been extensively used in the production of woods, papers, plastics, textiles, coatings, etc. (13-14).
  • the main purpose to add biocides into polymers is to protect the polymeric materials from deterioration and discoloration caused by microbial attacks (15-16). Therefore, some of the antimicrobial additives are actually preservatives, which have low antimicrobial activities and although antimicrobial are very toxic.
  • antimicrobial additives that protect both the polymers and the users has become an urgent issue; however, successful examples are still limited (13-16).
  • candidates of antimicrobial additives should meet the following requirements: they should be effective against a broad spectrum of microorganisms at low concentrations; they should have low toxicity to human, animals and the environment; they should be easily and inexpensively synthesized and processed; they should be compatible with the polymer, processing aids and other additives; they should have no negative impact on the properties and appearance of the polymers; they should be stable upon storage; and they should have long-lasting efficacy; etc. (14).
  • N-halamine vinyl compounds and their polymeric biocides are described. More particularly, heterocyclic vinylic compounds are described that may be used to form biocidal polymers.
  • the polymers may be used alone or grafted onto textiles, fabrics and polymers.
  • the polymers are readily converted to N-halamine structures on exposure to a halogen source such as commercially available chlorine bleach.
  • the N-halamine derivatives exhibit potent antibacterial properties against microorganisms and these properties are durable and regenerable.
  • United States Patent 6,762,225 issued to Malik, et al. , for light stabilizer composition and teaches a light stabilizer composition obtainable by mixing a polymer with at least one polyalkylpiperidine and at least one free radical generator and melt-blending of that mixture at a temperature above the melting point of the polymer and above the decomposition temperature of the free radical generator and at shear conditions sufficient to blend the components.
  • the light stabilizers of this patent provide a method for enhancing the light stability of polymers, preferably polyolefins.
  • United States Patent 6,670,412 issued to Erderly, et al. , for a method of melt processing amine containing polyethylenes and teaches a processed linear polyethylenes containing an amine additive are shown to exhibit improved processability through the addition of certain surfactants.
  • the amine compounds are generally one or more hindered amine light stabilizers, amine antistats, amine antioxidants or amine based UV inhibitors.
  • the melt processing parameters improved are reduced head pressure, reduced torque, reduced motor load, reduced or eliminated melt fracture, or combinations of these parameters.
  • WO 2005/058814 discloses a spiro compound, namely 7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione as a biocidal siloxane coating material to be coated on, attached to, or incorporated in a material to control and/or eliminate microorganisms. Said document was published on June 30, 2005, i.e. after the priority date of the present application.
  • the copolymer was ⁇ -irridiated up to 20 Mrad in air at room temperature, whereby progressive oxidation proceeded to form hydroperoxide and carbonyl groups, which were depressed by the antioxidizing action of the additives.
  • the apparent antioxidizing activity of LS-770 which is the non-halogenated compound, was higher than of LS-770-Cl, i.e. the halogenated compound.
  • SHAs Sterically Hindered Amines
  • piperidine derivatives which are widely available with low cost and low toxicity (14-18).
  • N-halo derivatives of SHAs could be readily synthesized by a simple halogenation reaction (19-20). Contrary to other halamines, hindered N-halamines prepared from SHAs are very stable and they were reported to be even better radiation stabilizers than their un-halogenated SHA precursors (21).
  • the SHA-based N-halamines additives of the present invention have been found to be powerful antimicrobial agents against both gram-negative and gram-positive bacteria.
  • the SHA-based N-halamines as novel antimicrobial additives may be used in conjunction with a wide range of polymeric materials.
  • compositions and methods are used to produce specific Sterically Hindered N-halo-amine-based antimicrobial polymers.
  • the antimicrobial polymer additive is a sterically hindered N-halo-amine including the moiety of 2,2,6,6-tetramethyl-N-chloro-4-piperidinyl structure, and has a molecular weight higher than 350 g/mol.
  • the present invention relates to antimicrobial polymer additives having a sterically selected from one or more of the following: Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-N-X-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidylimino]]; where R is C 11 -C 20 , predominantly C 16 -C 18 ; Poly[(6-morpholino-s-triazine-2,4-diyl)-N-X-[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]]; 1,2,3,4-Butanetetracarboxylic acid, polymer with ⁇ , ⁇ , ⁇ ', ⁇ '-
  • X is Cl or Br.
  • a source of halides may be, e.g., sodium di-X-isocyanurate, sodium hypohalite, N-X-succinimide, and calcium hypohalite, wherein X is selected from Cl or Br.
  • the additive may be mixed with polymeric materials prior to, or after halogenation reactions thereof.
  • the additive is an antimicrobial against gram-negative bacteria such as Escherichia coli (e.g., multi-drug resistant species, such as species that are resistant to sulfonamide) and gram-positive bacteria such as Staphylococcus aureus (e.g., multi-drug resistant species, such as species that are resistant to tetracycline, penicillin, streptomycin, and erythromycin) or species that are resistant to the mixtures and combinations or the drugs thereof.
  • the additive may be added to a polymer formed by extrusion, injection molding, hot pressing, coating, painting, solvent casting, mixtures and combinations thereof.
  • additive and polymers formed therewith include, e.g., a bead, a film, a tube, a sheet, a thread, a suture, a gauze, a bandage, an adhesive bandage, a vessel, a container, a cistern, a filter, filaments, yarns, a membrane, a coating, a paint and combinations thereof.
  • Sterically Hindered N-Halo-amines SHHs
  • Sterically Hindered Chloramines SHCs
  • the specific SHCs have potent, durable and rechargeable antimicrobial activities against both gram-negative and gram-positive bacteria and also has shown activity against a variety of pathogens including bacteria, virus, spores, fungi, bacteria phage and combinations thereof.
  • the additive is antimicrobial against gram-negative bacteria such as Escherichia coli (e.g., multi-drug resistant species, such as species that are resistant to sulfonamide), and gram-positive bacteria such as Staphylococcus aureus (e.g., multi-drug resistant species, such as species that are resistant to tetracycline, penicillin, streptomycin, and erythromycin), or species that are resistant to the mixtures and combinations or the drugs thereof.
  • gram-negative bacteria such as Escherichia coli
  • Staphylococcus aureus e.g., multi-drug resistant species, such as species that are resistant to tetracycline, penicillin, streptomycin, and erythromycin
  • Different methods may be used to physically add the specific SHCs into conventional and commercially important polymeric materials (e.g., plastics, rubbers, fibers, coatings, paints etc.) as antimicrobial polymer additives in the range of about 0.01 to about 30
  • SHHs are first synthesized from SHAs and then added into the polymer materials by solution blending and/or thermal blending.
  • the polymers are then processed into desired forms, e.g., a bead, a film, a tube, a sheet, a thread, a suture, a gauze, a bandage, an adhesive bandage, a vessel, a container, a cistern, a filter, a membrane, a coating, a paint and combinations thereof.
  • SHAs are added into the polymeric materials by solution and/or thermal blending.
  • the polymers are processed into desired forms, and then treated with halogen sources to transform the SHAs into SHHs, such as treated with chlorine bleach to transform the SHAs into SHCs.
  • Both methods can be readily used to incorporate the specific SHHs into conventional and commercially important polymers to transform them into antimicrobial polymeric materials.
  • the resultant polymeric materials demonstrate potent antimicrobial activities against both gram-negative and gram-positive bacteria.
  • the antimicrobial activity can be easily recharged by a simple halogen-treatment.
  • the antimicrobial activity may be recharged through the chlorination or bromination of pools and spas, washing, soaking or treating the material in a bleach, or treatment use in a water treatment systems including conduits and piping.
  • the present invention provides simple, practical, flexible, and cost-effective technologies to transform conventional and commercially important polymers into durable and rechargeable antimicrobial polymeric materials, which will find wide applications in medical devices, hospital equipment, water purification/delivery systems, food storage and packaging, hygienic products, consumer products, household items, bio-protective applications and other related challenging environments where self-decontamination of the polymeric material is needed.
  • acyl refers to those groups derived from an organic acid by removal of the hydroxy portion of the acid. Accordingly, acyl is meant to include, for example, acetyl, propionyl, butyryl, decanoyl, pivaloyl, benzoyl and the like.
  • R', R" and R'" each independently refer to hydrogen, and heteroalkyl, unsubstituted aryl, aryl substituted with halogens, unsubstituted alkyl, alkoxy or thioalkoxy groups, or aryl-(C 1 -C 10 )alkyl groups.
  • each of the R groups is independently selected as are each R', R" and R'" groups when more than one of these groups is present.
  • R' and R" are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 5-, 6-, or 7-membered ring.
  • heteroatom is meant to include oxygen (O), nitrogen (N), sulfur (S) and silicon (Si).
  • N-halo-amines are a class of novel rechargeable disinfectants, e.g., N-halamines.
  • N-halamine-based antimicrobial polymers are produced by three major methods, including functional modification of the polymers, (co)polymerization of polymerizable N-halamine precursors and grafting of polymerizable N-halamine precursors onto the target polymers.
  • Each of these technologies is suitable for the treatment of certain polymers, but a "universal" technology that can treat most conventional and commercially important polymeric materials has not been developed yet.
  • the current technologies involve one or more chemical modifications to prepare the final antimicrobial polymeric materials, which inevitably requires new/special steps and increases cost in the transformation of ordinary polymeric materials into antimicrobial polymers.
  • the present inventors recognized that these difficulties are part of the reasons why commercially important antimicrobial polymers have not been developed.
  • the specific sterically hindered N-halo-amines are physically mixed with conventional and commercially important polymeric materials as antimicrobial additives.
  • the target polymeric materials can be dissolved in solvent(s), or can be melted, they can be manufactured into SHHs-containing polymeric materials, providing durable and rechargeable antimicrobial activities.
  • dissolving and melting are conventional processing steps in the manufacturing of most polymeric materials, the present invention provides a universal technology to produce antimicrobial polymers.
  • SHHs can be painted or coated onto the polymeric materials.
  • the specific sterically hindered N-halo-amines used in the present invention are synthesized by a halogenation, e.g., chlorination, treatment of sterically hindered amines either before or after mixing with polymeric materials.
  • a halogenation e.g., chlorination
  • Sterically hindered amines are one of the most important photo-stabilizers of polymers, which are none or low toxic, widely available and relative inexpensive.
  • the present invention provides simple, practical, flexible and cost-effective approaches to transform conventional and commercially important polymers into antimicrobial polymeric materials.
  • the present invention will find widespread use in numerous areas of application.
  • soluble and/or meltable polymers can be manufactured into durable and rechargeable antimicrobial materials, and a wide range of surfaces can be transformed into durable and rechargeable antimicrobial materials by coating and or coating using this invention.
  • the present invention is also suitable for the treatment of plastics, rubbers, paints, coatings, and fibers, including, but not limited to, polyolefins, polystyrene and its derivatives, ABS, EPDM, cellulose acetate, polyurethane, etc.
  • the simple, practical, flexible and cost-effective sterically hindered N-halo-amines disclosed herein may be used as polymer additives in the range of about 0.01 to about 30.0 weight percent (wt%), the typical range is about 0.2 to about 5.0 wt%. Both solution and thermal blending can be used in the treatment.
  • the specific sterically hindered N-halo-amines can be formed before or after mixing. The present invention will find wide applicability because it requires no new treatment steps, training and/or new equipment used in the transformation of conventional and commercially important polymers into durable and rechargeable antimicrobial materials.
  • the applications for use of the present invention include, e.g. antimicrobial treatment of plastics, rubbers, paints, coatings and fibers.
  • the resulting materials may find applications in medical devices, hospital equipment, water purification/delivery systems, food storage and food packaging, hygienic products, consumer products, household items, bio-protective applications, and other related challenging environments where self-decontamination of the polymeric material is needed.
  • the specific sterically hindered N-halo-amines are derivatives of commercially available sterically hindered amines (SHAs) based light stabilizers derived from 2,2,6,6-tetramethylpiperidine (14-17).
  • SHAs sterically hindered amines
  • Commercially important SHAs have carefully designed and balanced structures to improve their compatibility with the target polymers to enhance long-term retention of the additive during ageing of the polymers.
  • the present invention uses commercially available SHAs based on 2,2,6,6-tetramethylpiperidine with a molecular weight higher than 350 g/mol; however the skilled artisan will recognize that polymers under 350 g/mol may also be used with the present invention.
  • SHAs used in this invention to produce antimicrobial SHHs Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-N-X-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidylimino]]; where R is C 11 -C 20 , predominantly C 16 -C 18 ; Poly[(6-morpholino-s-triazine-2,4-diyl)-N-X-[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]]; 1,2,3,4-Butanetetracarboxylic acid, polymer with ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-2,4,8,
  • Table 1 is a structural list of some of the commercially available SHAs that may be modified as disclosed herein.
  • the SHAs may be modified with halogen sources, e.g. Cl or. Br. Table 1.
  • the sterically hindered N-halo-amines may contain halogen atoms such as Cl or Br.
  • Table 2 is an exemplary structural list of sterically hindered N-halo-amines that contain Cl (SHCs) which may be used as disclosed herein. Table 2.
  • Example 1 SHC-2.
  • a solution of DCCANa (about 8.8 grams, 0.04 mol) in water (about 40ml) was added to a solution of about 5.95g (about 0.04 mol) SHA-2 in toluene (about 20ml).
  • the mixture was vigorously shaken for about 20 minutes.
  • Toluene (about 10 ml) was then added.
  • the precipitated cyanuric acid was filtered off.
  • the organic layer was separated from water and then dried under anhydrous CaCl 2 .
  • Example 2 SHC-3. A solution of DCCANa (about 8.8 grams, 0.04 mol) in water (about 40ml) was added to a solution of about 8.2 grams (about 0.04 mol) SHA-3 in toluene (about 20ml). The mixture was vigorously shaken for about 10 minutes. Toluene (about 10ml) was then added. The precipitated cyanuric acid was filtered off. The organic layer was separated from water. After the evaporation of toluene, the solid was collected and recrystallized from petroleum ether to produce a yield of about 79%, a melting point of about 32°C and an active chlorine content of about 7.86%.
  • Example 3 SHC-4. A solution of DCCANa (about 8.8g, 0.04mol) in water (about 40ml) was added to a solution of about 10.2 grams SHA-4 in toluene (about 20ml). The mixture was vigorously shaken for 20 minutes. Toluene (10ml) was then added. The precipitated cyanuric acid was filtered off. The organic layer was separated from water and then dried under anhydrous CaCl 2 .
  • FIGURE 1 illustrates another of the synthesis methods associated with the present invention.
  • the present invention provides that Poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (HALS-2) is be treated with sodium dichloroisocyanurate (DCCANa) to produce Poly[(6-morpholino-s-triazine-2,4-diyl)-N-chloro-[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (HALS-2-Cl).
  • HALS-2-Cl Poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-
  • Poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] is recharged to Poly[(6-morpholino-s-triazine-2,4-diyl)-N-chloro-[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] using a source of halides (bleach).
  • the bacteria used in this study are as follows: Escherichia coli, gram-negative, ATCC 15597; Staphylococcus aureus, gram-positive, ATCC 6538; Escherichia coli, gram-negative, resistant to sulfonamide, ATCC 29214; and Staphylococcus aureus subsp. aureus , gram-positive, resistant to tetracycline, penicillin, streptomycin, and erythromycin and ATCC 14154.
  • Staphylococcus aureus subsp. aureus , gram-positive, resistant to tetracycline, penicillin, streptomycin, and erythromycin and ATCC 14154.
  • Antimicrobial Procedure SHC samples were crushed into powders. A standard sieve was used to collect the powders in the 60-80 mesh (about 0.42-0.31mm) range. One gram of each sample was packed into a column (I.D.: about 6mm). About 1 ml of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL (colony forming units per milliliter) of the bacteria was passed through the columns containing the corresponding samples. The flow rate was controlled by compressed air (about 0.1-10 ml/min). The effluent was collected, serially diluted, and each dilution was placed onto nutrient agar plates. The same procedure was also applied to the un-chlorinated SHAs powders as control.
  • the SHC powders were neutralized by immersing in about 0.1 mol/L sodium thiosulfate solution at room temperature under shaking for about 30 minutes, and then chlorinated according to the synthesis procedures mentioned above. After each chlorination, the samples were washed thoroughly with a large amount of distilled water. The active chlorine contents of the SHC samples after about 50 cycles of "neutralization-chlorination" treatment were essentially unchanged.
  • SHA samples were added into polymeric materials by conventional processing technologies including extrusion, injection molding, thermal pressing, coating, painting or solvent casting. Then, the SHA-containing samples were halogenated to transfer SHAs into SHHs. In the second method, SHAs were first transferred into SHHs and then incorporated into commercially important polymers by extrusion, injection molding, thermal pressing, coating, painting or solvent casting. Both methods are feasible approaches to incorporate SHHs into polymeric materials and the resultant polymeric materials demonstrated potent, durable and rechargeable antimicrobial activities.
  • Example 4 Making SHA-containing PP Tubes. About 20 grams of PP pellets and about 0.8 grams SHA-3 powders (about 4 wt% of PP) were mechanically mixed and then extruded as a tube (I.D.: about 3mm, E.D.: about 5mm) from the Laboratory Mixing Extruder. The temperatures of the barrel and the die were kept at about 160 and 180°C respectively. The extruded PP tube from the die of the extruder was under the traction of the CSI-194T Take Up Apparatus.
  • Example 5 Making SHA-containing PE sheets. About 10 grams of PE pellets and about 0.02 grams of SHA-2 powders (about 0.2 wt% of PE) were mixed, homogenized for 5min, and then injection molded into a sheet of 1mm thickness. The machine used was a Minimax Laboratory Molder equipment with a test mould. The temperature of the mixing cup was about 160°C. Test mould was kept at ambient temperature.
  • Example 6 Solvent casting SHA-containing PS films. To about 70 ml chloroform containing about 7 grams PS pellets was added about 0.42 grams SHA-4 powders (about 6 wt% of PS), and then vigorously stirred. The sample solution was cast onto a clean glass surface. The PS films of about 200 ⁇ m thickness were formed after evaporation of solvent over night.
  • Transformation of SHA-containing plastics into SHC-containing plastics The additives of the present invention were formed into polymers by extrusion, injection molding, hot pressing and solvent casting/coating/painting as described hereinabove.
  • Example 7 PP extruded tubes containing about 4 wt% SHA-3 were chlorinated with a diluted household bleach (e.g., Clorox) containing about 0.6% sodium hypochlorite under constant shaking. The pH value and the chlorination time were kept at about 7.0 and about 1 hour, respectively. After chlorination, the PP tubes were thoroughly washed with a large amount of distilled water to remove free chlorine. The active chlorine content in the sample was about 159 ppm/gram determined by titration with 0.001 sodium thiosulfate solution.
  • a diluted household bleach e.g., Clorox
  • Example 8 PE injection molded sheets containing about 0.2 wt% SHA-2 were chlorinated with a diluted household bleach containing about 0.6% sodium hypochlorite under constant shaking. The pH value and the chlorination time were kept at about 9.0 and about 2 hours, respectively. After chlorination, the PE sheets were thoroughly washed with a large amount of distilled water to remove free chlorine. The active chlorine content in sample was about 120 ppm/gram determined by titration with about 0.001 sodium thiosulfate solution.
  • Example 9 PS solvent casting films containing about 6 wt% SHA-4 were chlorinated with a diluted household bleach (e.g., Clorox) containing about 0.6% sodium hypochlorite under constant shaking. The pH value and the chlorination time were kept at about 7.0 and about 4 hours, respectively. After chlorination, the PS films were thoroughly washed with a large amount of distilled water to remove free chlorine. The active chlorine content in samples was about 394 ppm/gram determined by titration with about 0.001 sodium thiosulfate solution.
  • a diluted household bleach e.g., Clorox
  • Antimicrobial activity of the SHC-containing materials as described hereinabove The polymeric materials were tested for antimicrobial properties using the following bacteria: Escherichia coli, gram-negative, ATCC 15597; Staphylococcus aureus, gram-positive, ATCC 6538; Escherichia coli, gram-negative, resistant to sulfonamide, ATCC 29214; and Staphylococcus aureus subsp. aureus , gram-positive, resistant to tetracycline, penicillin, streptomycin, and erythromycin, ATCC 14154.
  • Example 10 About 100 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL of the bacteria were dropped into the chlorinated PP extruded tube, whose bottom was sealed. The tube was shaken for a certain period of time. Then, the tube was put into about 100 mL of about 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted, and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • PP extruded tube containing about 159 ppm/gram of active chlorine inactivated about 90% of all the tested bacteria in a contact time of about 10 minutes. After about 60 min of contact time, the same tube provided total kill of the bacteria.
  • Example 11 About 10 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL bacteria was placed onto the surface of the chlorinated PE injection molded sheet (about 2x2 cm 2 ), and the sheet was covered with another identical sheet. After different contact time, the sheets were transferred into about 100 mL of about 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • PE injection molded sheet containing about 120 ppm/gram of active chlorine inactivated about 99.99% of all the tested bacteria in a contact time of less than about 30 seconds. After about 5 minutes of contact time, the same sheet provided total kill of the bacteria.
  • Example 12 About 10 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL bacteria was placed onto the surface of the chlorinated PS solvent casting film, and the film was covered with another identical film. After different contact time, the film was transferred into about 100 mL of about 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • Chlorinated polymer samples were treated in about 0.1 mol/L sodium thiosulfate solution at room temperature for about 30 minutes under constant shaking. After treatment, the samples were thoroughly washed with distilled water, and then bleached again according to the procedure described hereinabove. After each chlorination, the samples were washed thoroughly with a large amount of distilled water. The active chlorine contents of the samples after about 50 cycles of "neutralization-chlorination" treatments were essentially unchanged.
  • Extrusion Polymer tubes-Polymer pellets and SHC powders (about 0.01-30 wt% of the polymers) were extruded as tubes (I.D.: about 3mm, O.D.: about 5mm) from the Laboratory Mixing Extruder. The temperatures of the barrel and the die were kept at about 120-200 and about 140-200°C, respectively.
  • Fibers-Polymer pellets and SHC powders (about 0.01-30 wt% of the polymers) were extruded as fibers from the Laboratory Mixing Extruder.
  • the temperatures of the barrel and the die were kept at about 120-200 and about 160-200°C, respectively.
  • Injection molding Polymer sheets-Polymer pellets and SHC powders (about 0.01-30 wt% of the polymers) were mixed, homogenized and then injection molded into a sheet of 1mm thickness.
  • the machine used was a Minimax Laboratory Molder equipment with a test mould.
  • the temperature of the mixing cup was about 120-200°C. Test mould was kept at ambient temperature.
  • Hot pressing Polymer films-Polymer pellets and SHC powders (about 0.01-30 wt% of the polymers) were mixed and homogenized on a Minimax Laboratory Molder at about 120-200°C. Then the blended materials were hot pressed into a 300 ⁇ m thickness film at about 120-200°C using a hot press.
  • Solvent casting/painting/coating Polymer pellets and SHC powders (about 0.01-30 wt% of polymers) were dissolved in acetone, chloroform, THF, DMF or DMSO. The solution was cast, sprayed or brushed onto any surfaces. After evaporation of the solvent, films, coatings or paints were obtained.
  • Example 13 Making SHC-containing PP tubes. About 20 grams of PP pellets and about 0.8 grams SHC-3 powders (about 4 wt% of PP) were mechanically mixed and then extruded as a tube (I.D.: about 3mm, E.D.: about 5mm) from the Laboratory Mixing Extruder. The temperatures of the barrel and the die were kept at about 150 and 160°C respectively. The extruded PP tube from the die of the extruder was under the traction of a Take Up Apparatus. The active chlorine content in samples was about 105 ppm/gram determined by titration with about 0.001 sodium thiosulphate solution.
  • Example 14 Making SHC-containing PE sheets. About 10 grams of PE pellets and about 0.02 grams of SHC-2 powders (about 0.2 wt% of PE) were mixed, homogenized for about 2 minutes and then injection molded into a sheet of about 1 mm thickness. The machine used was a Minimax Laboratory Molder equipment with a test mould. The temperature of the mixing cup was about 145°C. Test mould was kept at ambient temperature. The active chlorine content in samples was about 88 ppm/gram determined by titration with about 0.001 sodium thiosulphate solution.
  • Example 15 Solvent casting SHC-containing PS Films. To about 70 ml chloroform containing about 7 gram PS pellets was added about 0.42 gram SHC-4 powders (about 6 wt% of PS), and then vigorously stirred. The sample solution was cast onto a clean glass surface. The PS films of about 200 ⁇ m thickness were formed after evaporation of solvent over night. The active chlorine content in samples was about 315 ppm/gram determined by titration with about 0.001 sodium thiosulphate solution.
  • the polymers were tested for antimicrobial properties using the following bacteria: Escherichia coli, gram-negative, ATCC 15597; Staphylococcus aureus, gram-positive, ATCC 6538; Escherichia coli, gram-negative, resistant to sulfonamide, ATCC 29214; and Staphylococcus aureus subsp. aureus , gram-positive, resistant to tetracycline, penicillin, streptomycin, and erythromycin and ATCC 14154.
  • Example 16 About 10 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL bacteria was dropped into the chlorinated PP extruded tube, whose bottom end was sealed. The tube was constantly shaken for a certain period of time. Then, the tube was transferred into about 100 mL of about 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • PP extruded tube containing about 105 ppm/gram of active chlorine inactivated about 90% of all the tested bacteria in a contact time of about 15 minutes. After about 120 minutes of contact time, the same tube provided total kill of the bacteria.
  • Example 17 About 10 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL bacteria was placed onto the surface of the chlorinated PE injection molded sheet (about 2x2 cm 2 ), and the sheet was covered with another identical sheet. After different contact time, the sheets were transferred into about 100 mL of 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • PE injection molded sheet containing about 88 ppm/gram of active chlorine inactivated about 99.99% of all the tested bacteria in a contact time of less than about 5 minutes. After about 15 minutes of contact time, the same sheet provided total kill of the bacteria.
  • Example 18 About 10 ⁇ L of an aqueous suspension containing about 10 6 ⁇ 7 CFU/mL bacteria was placed onto the surface of the chlorinated PS solvent casting film, and the film was covered with another identical film. After different contact time, the films were transferred into about 100 mL of about 0.03 wt% sodium thiosulfate aqueous solution. The resultant solution was vigorously shaken for about 5 minutes. An aliquot of the solution was serially diluted and about 100 ⁇ L of each dilution was placed onto nutrient agar plates. The same procedure was also applied to an un-chlorinated sample as a control. Viable bacterial colonies on the agar plates were counted after incubation at about 37°C for about 24 hours.
  • Chlorinated polymer samples e.g., films, sheets, coating, paints, and tubes
  • Chlorinated polymer samples were treated in about 0.1 mol/L sodium thiosulfate solution at room temperature for about 30 minutes under constant shaking. After treatment, the samples were thoroughly washed with distilled water, and then bleached again according to the procedure described above. After each chlorination the samples were washed thoroughly with a large amount of distilled water. The active chlorine contents of the samples after about 50 cycles of "neutralization-chlorination" treatments were essentially unchanged.
  • the applications for the present invention cover a spectrum of products, from healthcare professional uses to the broader areas of sanitation, infection and odor control in military and institutional hygienic practices.
  • the present invention also includes consumer uses especially in the hospitality industry, athletic wear and sports facilities sectors. These uses are fueled in recent times by an explosion of concern about new infectious disease problems, such as HIV/AIDS and avian influenza, the growing risk from antibiotic-resistant bacteria such as MRSA and VRE, and the age-old problems of hepatitis, tuberculosis, and E. coli .
  • the plastics and fabrics made using the present invention are anti-bacterial, anti-viral, anti-fungal and anti-odor with activity greater than silver-impregnated plastics and fabrics, the next-best approach.
  • the present invention includes plastic parts, films, tubing, cotton and synthetic fabrics and antimicrobial plastic additive that are antimicrobial in nature.
  • the plastic additive is compatible with standard plastics including PET, polyethylene, PVC, polypropylene, and polystyrene. Fiber and fabric manufacturers can use the plastic additive without altering their normal fiber extrusion process. Polyester; nylon, and polypropylene fabrics can now be made permanently antimicrobial.
  • low-melt-temperature plastics such as polystyrene, PVC and Polyethylene can be pre-chlorinated by adding the present invention to plastics to include non-woven fabrics, e.g., masks, wipes, shoe and head covers, diapers, wound care, and disposable healthcare fabrics, disposable medical plastics and packaging e.g., medical packaging to ensure sterility, food packaging to protect against bacteria, anti-mold packaging to extend shelf-life. Additional applications of the present invention are listed in Tables 6 and 7 below. Table 6 Antimicrobial Plastic Additive Product Examples Carpet & Upholstery • Healthcare carpeting. ⁇ Anti-infection (e.g., bacteria, viruses, and funguses). ⁇ Anti-odor. • Consumer carpeting for pet owners.
  • Non-Wovens Consumer Disposable Non-Wovens • Adult incontinence disposable diapers (e.g., anti-odor) • Baby diapers (e.g., anti-diaper rash) • Feminine hygiene products (e.g., tampons, pads) • Home wipers for cleaning Building Products • Biofilm remediation for plastic tubing and pipe applications in these markets: potable water storage, PVC potable water plumbing and piping in chlorinated systems (e.g., municipal and construction), medical tubing, dental tubing, manufacturing process water.
  • chlorinated systems e.g., municipal and construction
  • Anti-mold grout and caulk • Anti-mold wall board • Countertops and flooring • Anti-mold, antimicrobial paints and coatings • Low-cost water purification (low chlorine, antiviral) • Safe water storage (e.g., many uses such as the roof-top tanks ubiquitous in many parts of the world) • Military coatings.
  • the resultant polymeric materials of the present invention demonstrate potent antimicrobial and/or disinfectant activities against a variety of pathogens including bacteria, virus (e.g., retrovirus, herpesvirus, adenovirus, lentivirus, etc.), spores, fungi, bacteria phage and combinations thereof.
  • pathogens including bacteria, virus (e.g., retrovirus, herpesvirus, adenovirus, lentivirus, etc.), spores, fungi, bacteria phage and combinations thereof.
  • Bacteria includes but is not limited to Staphylococcus aureus (Staph), Salmonella choleraesuis, Pseudomonas aeruginosa, Streptococcus pyogenes (Strep), Escherichia coli 0157:H7 (E. coli), Shigella dysenteriae and combinations thereof.
  • viruses include but are not limited to polio virus, TT virus, herpes virus, hepatitis virus, or human immunodeficiency virus (HIV), HCV, HAV, HIV-1, HIV-2, HHV-6, HSV-1, HSV-2, CMV, EBV, rotavirus, adenoviruses, respiratory syncytial virus, Cytomegalovirus, parvovirus, Ebola virus, Varicella-zoster virus, poliovirus, Dengue virus, Haemophilus influenza, Influenza, Mycobacterium bovis (Tuberculosis), Rotavirus, Rubella virus, Rhinovirus (Cold virus), measles virus, mumps virus, influenza viruses and combinations thereof.
  • HCV human immunodeficiency virus
  • HAV human immunodeficiency virus
  • HIV-1 HIV-2
  • HHV-6 HSV-1
  • HSV-2 CMV
  • EBV rotavirus
  • adenoviruses adenoviruses
  • Fungi include but not limited to Candida albicans, Aspergillus, Blastomyces, Coccidioides, Cryptococcus, Epidermophyton, Histoplasma, Mucorales, Microsporum, Paracoccidioides brasiliensis, Sporothrix schenckii, Trichophyton,Trichophyton mentagrophytes and combinations thereof.
  • the present invention may be used to remove odors through antimicrobial and/or disinfectant activities against a variety of odor causing pathogens.
  • bacteria phage include but are not limited to Enterobacteria phage MS2, T4 bacteriophage, T1-T7 bacteriophage;, Mu phage, phage ⁇ X174, ⁇ phage, R17 phage, M13 phage, G4 phage, P1 phage, P2 phage N4 phage, ⁇ 6 phage and combinations thereof.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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EP06717982.0A 2005-01-03 2006-01-03 Method for transformation of conventional and commercially important polymers into durable and rechargeable antimicrobial polymeric materials Active EP1838772B1 (en)

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US20070062884A1 (en) 2005-08-11 2007-03-22 Board Of Regents, The University Of Texas System N-halamines compounds as multifunctional additives
US8486428B2 (en) 2006-03-27 2013-07-16 Board Of Regents, The University Of Texas System Compositions and methods for making and using acyclic N-halamine-based biocidal polymeric materials and articles
WO2009039180A2 (en) 2007-09-19 2009-03-26 Board Of Regents, The University Of Texas System Colorants based n-halamines compositions and method of making and using
US10570390B2 (en) 2011-08-19 2020-02-25 Rodney J. Y. Ho Compositions, devices, and methods for treating infections
CA2869634C (en) * 2012-05-17 2018-11-27 University Of Manitoba Biocidal compounds and methods for using same
US20160297911A1 (en) * 2013-12-03 2016-10-13 Nippon Soda Co., Ltd. Novel copolymer with cyclic halamine structure
CA2959032A1 (en) * 2014-08-28 2016-03-03 Jeffrey F. Williams Antimicrobial composition comprising an n-halamine and a halogen stabilizing compound
CN105289339B (zh) * 2015-11-16 2017-11-14 中国科学院长春应用化学研究所 一种抗菌超滤膜及其制备方法和膜再生方法
CA2992067C (en) * 2017-01-17 2023-07-04 Oxiscience Llc Composition for the prevention and elimination of odors
CN108863909A (zh) * 2018-08-03 2018-11-23 四川大学 一类新型卤胺结构化合物及其制备方法和抗菌领域应用
CN113150591B (zh) * 2021-02-24 2022-07-29 张元泽 一种水性涂料罐内防腐剂
EP4115890A1 (en) * 2021-05-07 2023-01-11 Daily Vita Limited Company Methods for inhibiting pathogenic infection and inhibiting growth of pathogens

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CN101123953B (zh) 2013-07-10
WO2006074455A2 (en) 2006-07-13
EA015480B1 (ru) 2011-08-30
EP1838772A2 (en) 2007-10-03
BRPI0606374A2 (pt) 2009-06-23
EP1838772A4 (en) 2010-12-01
JP2008526779A (ja) 2008-07-24
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